JP3349710B2 - Electrolyzer and electrolyzed water generator - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an electrolytic cell and an electrolyzed water generating apparatus for generating reducing electrolyzed water and other electrolyzed water which are preferable for use in drinking water, infusion solutions, injection solutions and the like.

BACKGROUND ART It has been reported that alkaline electrolyzed water obtained by electrolyzing water has a medical effect of suppressing abnormal fermentation and indigestion in the gastrointestinal tract, diarrhea, excessive gastric acid, etc.
It was thought that the cause was that mineral components such as calcium, sodium, magnesium, and potassium contained in the alkaline electrolyzed water were present as cations. Therefore, alkaline electrolyzed water for obtaining such a medical effect is controlled only by the contained metal ions and the pH value, and electrolyzes water added with calcium or the like until the pH reaches about 9 or more. It was generated by doing.

However, the disease is mainly caused by the fact that active oxygen generated in a living body oxidizes the biomolecule and damages the biomolecule. Such active oxygen is converted into non-toxic water by a reduction reaction with hydrogen ions. Can be returned to. If this reaction is further promoted, a medical effect will be exhibited. For this purpose, it is desirable to use electrolyzed water having a large oxidation-reduction potential (ORP) and a large absolute value (for example, an ORP of -300 mV or less). Has been found by the applicant's research.

By the way, this type of electrolytic water having a reducing property is used for drinking water,
When used for infusions, injections, dialysates, etc., it is desirable to maintain the pH as neutral as possible. However, in the conventional electrolyzed water generator, it was not possible to generate electrolyzed water having a neutral pH and a small redox potential on the negative side. That is, when water is electrolyzed by a conventional electrolyzed water generator, the pH and the ORP change in a correlated manner, and when the pH is increased to about 10, the ORP decreases to about -500 mV.
In electrolyzed water near neutrality such as ~ 8, the ORP is at least -1
It decreased only to about 50 mV. In other words, the conventional electrolyzed water generator could not control pH and ORP independently of each other.

DISCLOSURE OF THE INVENTION The present invention has been made in view of such problems of the related art, and has as its object to provide an electrolytic cell and an electrolyzed water generation device capable of controlling pH and ORP independently of each other. .

[1] In order to achieve the above object, the electrolytic cell of the present invention includes an electrolysis chamber into which raw water to be electrolyzed is introduced, and at least one pair of electrolysis chambers provided between the electrolysis chamber and the outside of the electrolysis chamber with a diaphragm interposed therebetween. An electrode plate, wherein the electrode plate outside the electrolytic chamber is provided in contact with the diaphragm or with a slight gap therebetween.

In the electrolytic cell of the present invention, a pair of electrode plates is provided in each of the electrolytic chamber and the outside of the electrolytic chamber with a diaphragm interposed therebetween, and one electrode plate is provided outside the diaphragm with a contact or a slight gap. Then, electrolysis is performed by passing a current through the electrode plate pair while flowing raw water into the electrolysis chamber.

Here, between the electrode plate pair provided across the diaphragm, especially between the electrode plate and the diaphragm outside the electrolytic chamber, the raw water to be electrolyzed is due to the water content of the diaphragm and the capillary phenomenon between the electrode plate and the diaphragm. Because of the interposition, a current flows between the two electrode plates.

The chemical reaction occurring at this time will be described in the case where the electrode plate inside the electrolytic chamber is minus and the electrode plate outside the electrolytic chamber is plus.

First, when a DC voltage is applied to the electrode plate pair, a reaction of 2H ₂ O + 2e ⁻ → 2OH ⁻ + H ₂ ↑ (1) occurs on the surface of the cathode plate in the electrolysis chamber, and the surface of the electrode plate outside the electrolysis chamber across the diaphragm. That is, a reaction of H ₂ O−2e ⁻ → 2H ^{+ +} 1/2 · O ₂ … (2) occurs between the electrode plate and the diaphragm.

In the electrolytic cell of the present invention, since the diaphragm and the electrode plate (anode) outside the electrolytic chamber are almost in contact with each other, the H ⁺ ions of the above formula (2) (actually, oxonium ions H ₃ O ⁺
Exists in the form of ) Is strongly repelled by the anode plate, and a relatively large electric force is applied in the direction of the diaphragm. This allows H ⁺ ions to pass through while being impregnated in the diaphragm,
A part thereof receives the electron e ⁻ from the cathode plate and becomes a hydrogen gas as shown in the following formula (3) and dissolves in the generated electrolysis water on the cathode side.

2H ⁺ + 2e ⁻ → H ₂ … (3) As a result, the electrolyzed water generated on the cathode side (that is, the electrolytic chamber) has a lower oxidation-reduction potential (ORP) than usual (O
Electrolyzed water with a negative RP and a large absolute value is also referred to as electrolytic reduced water. ).

Incidentally, the remaining H ⁺ ions passing through the diaphragm react with OH ⁻ ions in the electrolytic chamber and return to water (2H ⁺ + OH ^−).
→ H ₂ O), the pH of the electrolytically reduced water generated in the electrolytic chamber will approach slightly neutral.

[2] In the electrolytic cell of the present invention, if at least two pairs of the diaphragm and the electrode plate are provided, at least two electrode plates are provided in the electrolytic chamber. The reaction of the above formula (1) proceeds. Therefore, compared with the case where a pair of electrode plates are provided with the diaphragm interposed therebetween, the electrolytic reaction area per unit volume increases,
Electrolysis efficiency is improved, and the electrolytic cell can be made compact.

Further, in the electrolytic cell of the present invention, the diaphragm and the electrode plate (anode) outside the electrolytic chamber are provided almost in contact with each other, and only water interposed between the diaphragm and the electrode plate outside the electrolytic chamber serves as a current-carrying medium. The oxygen gas generated by the above equation (2) is released to the atmosphere as it is. Therefore, as compared with so-called diaphragmless electrolysis, the amount of dissolved oxygen in the generated electrolytic water is significantly reduced, and the oxidation-reduction potential is further reduced.

At the same time, when the H ⁺ ions and oxygen gas on the right side of the above equation (2) are discharged from between the diaphragm and the electrode plate outside the electrolytic chamber, the reaction in the right direction of the equation (2) from the point of chemical equilibrium. Tend to be active. As a result, water molecules H ₂
The ability to donate electrons to O and the ability to accept electrons from the water molecules H ₂ O on the anode plate are activated, so that even if electrolysis is performed for a long time, the amount of electricity does not decrease and stable electrolytic water Can be obtained.

In the electrolytic cell of the present invention, when at least two pairs of the diaphragm and the electrode plate are provided, it is more preferable that any one of at least two electrode plates provided outside the electrolytic chamber is provided in the second electrolytic chamber. . Then, raw water to be electrolyzed (an electrolyte may be added as necessary) is supplied to the second electrolysis chamber, and the above-described original electrolysis chamber (hereinafter also referred to as a first electrolysis chamber for convenience). The electrolysis is carried out by supplying a current to each of the two pairs of electrode plates while flowing the raw water to be electrolyzed in the above (1).

Here, the case where the electrode plate inside the first electrolytic chamber is minus and the electrode plate outside the first electrode chamber is plus will be described as an example. The anode plate provided in the second electrolytic chamber is paired with the anode plate. For the electrolysis performed between the cathode plate and the cathode plate, sufficient raw water to be electrolyzed is supplied to both electrolysis chambers.
R also decreases, and mineral components are further condensed.

On the other hand, the electrolysis performed between the other anode plate and the cathode plate paired with the other anode plate is generated near the cathode plate because the chamber provided with the anode plate is open to the atmosphere. Although the pH of the electrolytically reduced water does not increase so much and the mineral components do not change, the ORP decreases for the above-mentioned reason.

Generally, the ORP of the electrolyzed water can be easily lowered as the pH is higher. Therefore, it is advantageous to increase the pH when it is desired to generate electrolyzed water having a large reduction potential.

As described above, since there is an electrode plate pair that generates electrolyzed water having different physical property values in one electrolytic cell, the pH and the OR are controlled by appropriately controlling these electrode plate pairs as needed.
P can be controlled without being affected by differences in the quality (pH and ORP) of the raw water to be electrolyzed.

In this case, the first electrolysis chamber and the second electrolysis chamber into which the raw water to be electrolyzed is introduced and partitioned by the diaphragm, and the first electrolysis chamber and the second electrolysis chamber are provided with the diaphragm interposed therebetween. A first electrolytic cell having at least a pair of electrode plates, a third electrolytic chamber into which electrolytic water generated in the first electrolytic chamber of the first electrolytic cell is introduced, and a third electrolytic cell. At least one pair of electrode plates provided with an intervening membrane between the electrolysis chamber and the outside of the third electrolysis chamber, respectively, and the electrode plate outside the third electrolysis chamber is in contact with the intervening membrane or through a slight gap. By providing an electrolytic cell having a second electrolytic cell provided, the degree of freedom of the combination of pH and ORP can be further increased.

[3] Although not limited to the electrolytic cell of the present invention, as a method for back washing the electrolytic cell, for example, a voltage of either an anode or a cathode is applied to one of the electrode plates provided in the electrolytic chamber, After applying the voltage of either the anode or the cathode to the other, and performing the first reverse cleaning, it is preferable to perform the second reverse cleaning by reversing the polarity of the voltage applied to the electrode plate. At this time, although not particularly limited, it is preferable that no voltage is applied to the electrode plate provided outside the electrolytic chamber during the first and second backwashing.

The general method of backwashing is to simply reverse the polarity of the applied voltage and apply the anode to the electrode plate on which the cathode has been applied to which the scale has been attached, thereby electrically eluting the attached scale. Therefore, it is possible to adopt such a back washing method also in the above-described electrolytic cell of the present invention.

However, even during the back washing, the scale adheres to the electrode plate to which the cathode is applied. In the above-described electrolytic cell of the present invention, when the anode is applied to this electrode plate after the transition to the positive electrolysis, the raw water to be electrolyzed is not supplied to the electrode plate, so that the scale once adhered is difficult to remove. For this reason, by using at least two electrode plates provided in the first electrolysis chamber, a scale that adheres to these electrode plates is removed by applying a reverse cleaning current only to the electrode plates.

In this case, the scale does not adhere to the electrode plate provided outside the first electrolysis chamber, and the backwash can be performed by applying a current only to the electrode plate provided inside the first electrolysis chamber. And if the current is the same, the backwashing time can be reduced by half.

[4] Although the above-described electrolytic cell of the present invention can be used alone, a plurality of electrolytic cells, a water supply system for introducing raw water in parallel to each electrolytic chamber of the electrolytic cell, and a water supply system generated in each of the electrolytic chambers. It can also be configured as an electrolyzed water generating apparatus, which is provided with a water intake system for taking out electrolyzed water in parallel.

In the electrolytic cell and the electrolyzed water generating apparatus of the present invention, the electrode plate outside the electrolytic chamber is provided in contact with the diaphragm or with a small gap therebetween, but this concept includes forming an electrode film on the surface of the diaphragm. is there.

The membrane used in the electrolytic cell and the electrolyzed water generator of the present invention is not particularly limited, and examples thereof include a porous membrane, a cation exchange membrane, and an anion exchange membrane. In short, the membrane according to the present invention only needs to have at least porosity and water content through which water molecules can pass.

Further, in the electrolytic cell and the electrolyzed water generator of the present invention, another conductor or semiconductor can be laminated on the main surface of the electrode plate facing the diaphragm. In the present invention, these are referred to as an electrode plate.

The use of the electrolyzed water generated by the electrolyzer and the electrolyzed water generation device of the present invention is not particularly limited, and can be applied to a wide range of fields such as a medical field, a food field, an agricultural field, and an industrial field in addition to a drink and a medical field. Can be applied.

In addition, the electrolyzed water obtained by the electrode tank and the electrolyzed water generation device of the present invention is characterized in that the value of the oxidation-reduction potential does not depend on pH. With electrolytic reduced water instead of alkaline electrolytic water,
The electrolytic water generated on the anode side is referred to as electrolytic oxidized water instead of electrolytic oxidized water.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view showing a first embodiment of the present invention, FIGS. 2 and 3 are cross-sectional views for explaining a reverse cleaning method of the first embodiment, and FIG. FIG. 5 is a system diagram showing a third embodiment of the present invention, FIG. 6 is a cross-sectional diagram showing a fourth embodiment of the present invention, and FIG. 7 is a graph showing a change in pH with respect to a continuous operation time. FIG. 8 is a graph showing changes in ORP with respect to continuous operation time, FIG. 9 is a longitudinal sectional view showing a conventional electrolytic cell used as a comparative example, and FIG. 10 is a longitudinal sectional view showing a specific example of the fourth embodiment of the present invention. FIG. 11, FIG. 11 is a longitudinal sectional view showing another specific example of the fourth embodiment of the present invention, FIG. 12 is a longitudinal sectional view showing a fifth embodiment of the present invention, and FIG. 13 is a sixth embodiment of the present invention. FIG. 14 is a sectional view showing another example of the diaphragm and the electrode according to the present invention, and FIG. 15 is a modification of the second embodiment. FIG.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described with reference to the drawings.

[First Embodiment] Fig. 1 is a longitudinal sectional view showing a first embodiment of the present invention,
1 shows a basic structure of an electrode tank of the present invention.

The electrolytic cell 11 of the present embodiment has an inlet 11 for introducing raw water.
1 and an outlet 112 for taking out the generated electrolyzed water are formed, and an electrolytic chamber 113 is formed between the inlet 111 and the outlet 112. Although not particularly limited, in the electrolytic cell 11 of the present example, an inlet is provided on the bottom surface of the casing 114 so that raw water is introduced in a direction perpendicular to the plane of the drawing.
An outlet 11 is formed on the top surface of the casing 114 so that electrolyzed water is taken in a direction perpendicular to the plane of the drawing.
2 are formed.

Further, a porous diaphragm 115 is provided on the left and right side walls of the electrolytic cell 11, and the electrode plate 1
16 are provided in contact with each other. The other electrode plate 117
Are provided in the electrolytic chamber 113 such that their main surfaces face one of the electrode plates 116, respectively.

A DC power supply 12 is connected to the two pairs of electrode plates 116 and 117, and a pair of electrode plates 11 opposed to each other with a diaphragm 115 interposed therebetween.
An anode is applied to one of 6.117 and a cathode is applied to the other electrode plate. For example, when producing electrolytic reduced water in the electrolytic chamber 113, as shown in FIG.
A cathode of a DC power supply is connected to an electrode plate 117 provided inside 113, and an anode is connected to an electrode plate 116 provided outside electrolysis chamber 113.

When electrolytic oxidized water is generated in the electrolytic chamber 113, an anode of a DC power supply is connected to an electrode plate 117 provided in the electrolytic chamber 113, and a cathode is connected to an electrode plate 116 provided outside the electrolytic chamber 113. Should be connected.

It is preferable that the diaphragm 115 used in the present embodiment has a property that the water flowing into the electrolytic chamber 113 easily permeates and the permeated water does not easily drip. That is, the electrolytic cell of the present embodiment
In 11, a water film is formed in the diaphragm 115 itself and in a slight gap S between the diaphragm 115 and the electrode plate 116 during electrolysis, and a current flows through the electrode plates 116 and 117 via the water film. Therefore,
It is important that the water constituting the water film is sequentially replaced in order to increase the electrolysis efficiency. Further, if water that has permeated into the diaphragm 115 leaks from between the diaphragm 115 and the electrode plate 116, the water must be treated. Therefore, it is preferable that the water has such a water content that the permeated water does not drip.

As an example of the diaphragm 115, the aggregate is a polyester nonwoven fabric or a polyethylene screen, the membrane material is chlorinated ethylene or polyvinylidene fluoride and titanium oxide or polyvinyl chloride, the thickness is 0.1 to 0.3 mm, and the average pore diameter is 0.
For example, a porous membrane having a water permeability of 1.0 cc / cm ² · min or less and a water permeability of 1.0 to 1.0 μm can be exemplified.

On the other hand, the distance between the pair of electrode plates 116 and 117 that are disposed to face each other with the diaphragm 115 interposed therebetween is 0 mm to 5.0 mm, and more preferably 1.5 mm. Here, the distance between the electrode plates 116 and 117 is 0 mm, for example, as shown in FIG. 14, when a zero gap electrode in which an electrode film is directly formed on each of both main surfaces of the diaphragm 115 is used, and substantially. Means that a distance equal to the thickness of the diaphragm 115 is provided. Zero gap electrode is diaphragm 11
The electrode may be formed only on one of the main surfaces of No. 5. When such a zero-gap electrode is employed, it is desirable to provide holes or gaps in the electrode plates 116 and 117 for allowing gas generated from the electrode surface to escape to the back side opposite to the diaphragm 115.

The distance between the electrode plates 117 provided in the electrolytic chamber 113 is not particularly limited, but is 0.5 mm to 5 mm, and more preferably 1 mm.

When producing electrolytic reduced water using such an electrolytic cell 11, first, two electrode plates 1 provided in the electrolytic chamber 113 are provided.
Connect the cathode (-) of DC power supply 12 to 17,117,
The anode (+) of the DC power supply 12 is connected to the electrode plates 116, 116 provided outside the electrolytic chamber 113, and a voltage is applied to the two pairs of electrode plates 116, 117 opposed to each other across the diaphragm 115. Then, when water such as tap water is introduced from the inlet 111, tap water is electrolyzed in the electrolysis chamber 113, and the above-described equation (1) reaction occurs on and near the surface of the electrode plate 117. In addition, the above-described reaction (2) occurs on the surface of the electrode plate 116 outside the electrolytic chamber 113 across the diaphragm 115, that is, between the electrode plate 116 and the diaphragm 115.

The H ⁺ ions pass therethrough while being contained in the diaphragm 115, and a part of the H ⁺ ions receive electrons e ⁻ from the cathode plate 117 and become hydrogen gas to be dissolved in the electrolyzed water on the cathode side. As a result, the electrolyzed water generated on the cathode side (that is, in the electrolysis chamber 113) becomes electrolyzed water having a lower oxidation-reduction potential (ORP) than usual.

In addition, the remaining H ⁺ ions that have passed through the diaphragm 115
Since the water reacts with the OH ^- ions in 13 and returns to water, the pH of the electrolytically reduced water generated in the electrolytic chamber 113 becomes slightly neutral. That is, electrolytically reduced water having a low ORP but a low pH is obtained. The electrolytic reduced water containing hydroxide ions generated in this way is supplied from the outlet 112.

When electrolysis is continued using tap water as raw water to be electrolyzed, calcium ions and magnesium ions contained in the tap water precipitate on the surface of the cathode plate 117, and this becomes a scale, which causes a reduction in electrolysis efficiency. For this reason, after performing electrolysis for a certain period of time, so-called reverse cleaning is performed, in which the scale deposited on the cathode plate 117 is removed.
Also for the electrolytic cell 11 of the present embodiment, such back washing is performed at certain intervals.

As the simplest method of back washing, a method of simply reversing the polarity applied so far can be considered. That is, regarding the case where the alkaline electrolyzed water is generated as described above, two electrode plates 117 and 117 provided in the electrolysis chamber 113 are provided.
Connect the anode (+) of the DC power supply 12 to the
The cathode (-) of the DC power supply 12 is connected to the electrode plates 116 and 116 provided outside the 113, and a voltage is applied to two pairs of electrode plates 116 and 117 opposed to each other across the diaphragm 115. As a result, the electrode plate 117 to which the cathode was
In, the attached positive metal ions are eluted into tap water by application of the anode, and are discharged from the outlet 112.

In the electrolytic cell of the present invention, such a back washing method can of course be adopted, but the electrode plate 1 provided outside the electrolytic chamber 113 can be used.
When a cathode is applied to the electrode plate 16, the electrode plate 11 is
As a result, the scale deposited on the electrode plate 116 is difficult to remove in the subsequent positive electrolysis with the structure shown in FIG. If this is continued, the scale that deposits on the electrode plate 116 will increase due to removal, and there is a possibility that the electrolytic efficiency will decrease.

Therefore, the back washing according to the present embodiment is performed, as shown in FIGS. 2 and 3, by using two electrode plates 117 and 117 provided in the electrolytic chamber 113.
The voltage is applied only to the scale to remove the scale. That is, first, as shown in FIG. 2, the polarity of one of the two electrode plates 117 and 117 provided in the electrolysis chamber 113 (here, the left electrode plate 117) is directly set to minus,
The polarity of the other (here, the right electrode plate 117) is inverted, and a positive voltage is applied. As a result, in the electrolysis chamber 113, a current flows between the two electrode plates 117, 117, and the scale deposited on the right electrode plate 117 to which the positive voltage is applied elutes into tap water.

After this is continued for a certain period of time, the applied polarities of the two electrode plates 117 are reversed as shown in FIG. In other words, by applying a positive voltage to the left electrode plate 117 and a negative voltage to the right electrode plate 117 and passing a current between the two electrode plates 117, 117, the scale deposited on the left electrode plate 117 is removed. I do.

By adopting such a back washing method, the power consumed at the time of back washing is halved, or if the same power consumption is used, the back washing time is halved. Also, since no current is supplied to the electrode plate 116 provided outside the electrolytic chamber 113 at the time of back washing,
Only the anode voltage is applied to the electrode plate 116. Therefore, from the viewpoint of durability performance, it is not necessary to use an expensive plate material that can be used in both electrodes, or the thickness can be reduced when a noble metal coating is applied.

By the way, in the above-described embodiment, the electrolytic cell 11 of the present invention has been described by taking as an example the case where electrolytic reduced water is generated, but the electrolytic cell 11 of the present invention can also be applied to the case of generating electrolytic oxidized water. In this case, the anodes (+) of the DC power supply 12 are connected to the two electrode plates 117, 117 provided in the electrolytic chamber 113, and the cathodes of the DC power supply 12 are connected to the electrode plates 116, 116 provided outside the electrolytic chamber 113. (−) May be connected, and a voltage may be applied to two pairs of electrode plates 116 and 117 opposed to each other with the diaphragm 115 interposed therebetween.

Then, when water such as tap water is introduced from the inlet 111, tap water is electrolyzed in the electrolytic chamber 113, and the electrode plate 1
While the reaction of the above formula (2) occurs on the surface of the electrode 17 and in the vicinity thereof, on the surface of the electrode plate 116 outside the electrolytic chamber 113 across the diaphragm 115, that is, on the water film between the electrode plate 116 and the diaphragm 115 Causes the reaction of the above-described formula (1).

The OH ^- ions pass therethrough while being contained in the diaphragm 115, and a part of the OH ^- ions transfer the electrons e ^- to the cathode plate 117, become oxygen gas, and dissolve in the electrolyzed water on the anode side. Thus, the electrolyzed water generated on the anode side (that is, in the electrolysis chamber 113) becomes electrolyzed oxidized water having a higher oxidation-reduction potential (ORP) than usual.

In addition, the remaining OH 2 ^- ions that have passed through the diaphragm 115
Since it reacts with H ⁺ ions in 113 and returns to water, the pH of the electrolytic oxidized water generated in the electrolytic chamber 113 becomes slightly neutral. That is, electrolytic oxidized water having a low ORP but a high ORP is obtained. The electrolytic oxidized water containing hydrogen ions thus generated is supplied from the outlet 112.

 The electrolytic cell 11 of the present embodiment will be described more specifically.

Using an electrolytic cell 11 having the basic structure shown in FIG.
7.9, ORP flow of + 473mV tap water at 4L / min.
14A by applying a voltage to the electrode plates 116 and 117 with an area of 24 cm ²
The electrolysis was performed at a constant current of.

Further, as the diaphragm 115, the aggregate is a polyester non-woven fabric,
The film material is polyvinylidene fluoride and titanium oxide, and the thickness is 0.
A porous membrane having a diameter of 12 mm, an average pore diameter of 0.4 μm, and a water permeability of 0.3 cc / cm ² · min or less was used. The distance between the electrode plates 116 and 117 was 1 mm, and the distance between the electrode plates 117 and 117 was 1 mm.

As a result, immediately after generation, pH = 9.03, ORP = −550.
mV electrolytic reduced water was obtained. The electrolytically reduced water was allowed to stand, and the pH and ORP after 5, 10 and 30 minutes were measured. The results are as shown in Table 1.

According to this, the pH exceeded 9 at the beginning of electrolysis, but the pH immediately dropped and was stabilized at pH = 8. This is the diaphragm
H ⁺ ions generated in the water film between the
5 and moved to the electrolysis chamber 113, where OH ⁻
It is considered that the cause is a neutralization reaction with ions.

[Second Embodiment] The electrolytic cell of the present invention has the basic structure shown in Fig. 1, but various forms can be considered for implementation. FIG. 4 is a longitudinal sectional view showing a second embodiment of the present invention, and members common to the basic structure of the electrolytic cell 11 of the present invention shown in FIG.

In the electrolytic cell 11 of the present embodiment, one of the electrode plates 116, 116 provided outside the electrolytic chamber 113 (here, the left side)
However, the second embodiment is different from the first embodiment in that the second electrolysis chamber 118 is provided. The second electrolysis chamber 118 is formed on one side wall of the casing 114, and the raw water to be electrolyzed is introduced into the second electrolysis chamber 118. The introduction of the raw water to be electrolyzed into the second electrolysis chamber 118 may be performed by passing water or simply by filling the raw water to be electrolyzed.

According to such an electrolytic cell 11, the electrolytically reduced water generated by the right electrode plate pair 116 and 117 is p as described above.
ORP can be specifically increased to the minus side without increasing H significantly. On the other hand, the electrolytic reduced water generated by the left electrode plate pair 116 and 117 has a large pH and ORP
Also increases to the negative side.

Therefore, a mixture of these two types of electrolytic reduced water is taken from the outlet 112 of the electrolytic cell 11, so that the right electrode plate pair 116 and 117 and the left electrode plate pair 116
By controlling the current flowing to each of
The combination of H and ORP can be adjusted arbitrarily.

This is particularly effective when the quality of the raw water to be electrolyzed is different. For example, the balance of the pH and ORP of the raw water to be electrolyzed often varies greatly depending on the region and the season.In such a case, if the electrolytic cell 11 of the present embodiment is used, the balance between pH and ORP is set to a desired value. Can be controlled.

 The electrolytic cell 11 of the present embodiment will be described more specifically.

Using an electrolytic cell 11 having the basic structure shown in FIG.
7.9, 4 liters / m of tap water with ORP of +473 mV in electrolysis chamber 113
1 l / min into the second electrolysis chamber 118
Then, voltage was applied to one electrode plate 116, 117 having an area of 24 cm ² , and electrolysis was performed at a constant current of 7A.

Further, as the diaphragm 115, the aggregate is a polyester non-woven fabric,
The film material is polyvinylidene fluoride and titanium oxide, and the thickness is 0.
A porous membrane having a diameter of 12 mm, an average pore diameter of 0.4 μm, and a water permeability of 0.3 cc / cm ² · min or less was used. The distance between the electrode plates 116 and 117 was 1 mm, and the distance between the electrode plates 117 and 117 was 1 mm.

As a result, immediately after production, pH = 9.57, ORP = −657.
mV electrolytic reduced water was obtained. The electrolytically reduced water was allowed to stand, and the pH and ORP after 5 minutes and 10 minutes were measured. The results are as shown in Table 2.

Next, in FIG. 4, current values flowing through a pair of electrode plates 116 and 117 provided in the second electrolytic chamber 118 are set to 3 A and 5 A, respectively.
Electrolyzed water was produced under the same conditions as above. Table 2 shows the results.
Shown in

According to this, it is possible to generate electrolyzed water having a desired pH and ORP by appropriately adjusting the current value flowing through the electrode plate pair.

As a modification of the above-described second embodiment, it is conceivable to connect two or more electrolytic cells in series. For example, Figure 15
The electrolytic cell 11 shown in FIG. 1 is a general water-flow type electrolytic cell 11A (first electrolytic cell) and the electrolytic cell 11B of the first embodiment (second electrolytic cell).
Are connected in series.

An inlet 111A into which raw water to be electrolyzed such as tap water is introduced is formed at one end of a casing 114A of the first electrolytic cell 11A, and a pair of electrode plates sandwiching a diaphragm 115A is formed in the casing 114A. 116A and 117A are provided. In this example,
Two pairs of diaphragms 115A and electrode plates on both sides of casing 114A
116A and 117A are provided. Thereby, two diaphragms 1
An electrolytic chamber 113A is formed between 15A and 115A, and a diaphragm is formed.
Second electrolytic chambers 118A, 118A are formed outside 115A, 115A.

The casing 114A located downstream of the second electrolysis chamber
Is provided with an outlet 118Aa for discharging the electrolyzed water generated in the second electrolysis chamber 118A to the outside of the system.

The electrolytic cell 11B of the above-described first embodiment (see FIG. 1) is connected to the downstream side of the first electrolytic cell 11A, and the same members are denoted by the same reference numerals.

As shown in FIG. 15, the first electrolytic cell 11A and the second electrolytic cell 1
1B is connected in series, and electrolytic reduction water having a small ORP is generated in the electrolytic cell 11. First, electrolytic water having a large pH (alkaline) is generated in the first electrolytic cell 11A, and this is used as raw water to be electrolyzed. When the ORP is introduced into the second electrolytic cell 11B, the ORP can be increased mainly in the negative direction in the second electrolytic cell 11B. That is, the pH can be adjusted in the first electrolytic cell 11A, and the ORP can be adjusted in the second electrolytic cell 11B. Further, electrolyzed water having a high degree of freedom in combination of pH and ORP can be obtained. .

Third Embodiment FIG. 5 is a system diagram showing an embodiment of an electrolyzed water generation device 1 configured using the above-described electrolyzer 11 of the present invention. The electrolyzer 11 of the above-described first or second embodiment is shown. Are connected in parallel, and a water supply system 13 for supplying raw water to be electrolyzed is provided at each of the inlets 111 of the electrolytic cell 11.

The water supply system 13 includes a main water supply pipe 131 and a plurality of branch water supply pipes 132 branched from the main water supply pipe 131.The main water supply pipe 131 is provided with a strainer 133 for filtering foreign substances in the water to be electrolyzed. Is provided with a manual valve 134 to constitute a drain.

Each branch water supply pipe 132 has a pressure reducing valve 135 and a solenoid valve 136.
Is provided, and is further branched at this point.
And a manual valve 138 is provided.

On the other hand, a water intake system 14 is provided at the outlet 112 of the electrolytic cell 11 provided in parallel. This water intake system 14 is
Main intake pipe 141 that aggregates each outlet 112
, An electric valve 142 provided at the tip thereof, a drain pipe 143 branched from the main water intake pipe 141, and an electric valve 144 provided in the drain pipe 143.

Although not shown, a DC power supply 12 shown in FIG. 1 or 4 is connected to each electrolytic cell 11.

In order to generate the desired electrolyzed water using the electrolyzed water generating apparatus 1, first, the manual valves 134 at the tips of the main water supply pipes 131 are closed, and the manual valves 138 of the branch water supply pipes 132 are opened. Then, raw water is supplied to the main water supply pipe 131, and the solenoid valve 136 of each branch water supply pipe 132 and the electric valve 142 of the water intake system 14 are controlled.

Although not particularly limited, as one example of the operation method, it is preferable to sequentially backwash any one of the electrolytic cells 11. In other words, when any one of the electrolytic cells 11 is constantly being backwashed and the remaining electrolytic cells 11 are controlled to generate electrolytic water, the quality of the electrolytic water taken out by the water intake system 14 is always constant. .

Fourth Embodiment FIG. 6 is a cross-sectional view showing a fourth embodiment of the electrolytic cell of the present invention, and members common to the basic structure of the electrolytic cell 11 shown in FIG. is there. This example is different from the first embodiment in that only a pair of the diaphragm 115 and the electrode plates 116 and 117 are provided.

Even if such an electrolytic cell 11 is used, basically the first
Although the same operational effects as those of the embodiment can be obtained, the present embodiment will be described more specifically.

As Example 1, electrolysis was performed by using an electrolytic cell having a basic structure shown in FIG. 6 and flowing tap water having a pH of 7.2 and an ORP of +450 mV at 4 L / min, and applying a voltage of 30 V.
The current flowing through both electrode plates 116 and 117 was 4 A (120 W).
Further, as the diaphragm 115, the aggregate is a polyester nonwoven fabric, the membrane material is polyvinylidene fluoride and titanium oxide, and the thickness is 0.12.
mm, a porous membrane having an average pore diameter of 0.4 μm and a water permeability of 0.3 cc / cm ² · min or less was used, and the distance between the electrode plates 116 and 117 was 1 mm.

As a result, electrolytically reduced water having a pH of 8 to 9 and an ORP of -220 mV was obtained. This electrolysis was continued for 1 hour.
As shown in and 8, the pH and ORP values hardly changed (see Example 1). As shown in FIG. 7, electrolyzed water having a pH of more than 9 was obtained in the initial stage of electrolysis, but the pH immediately dropped and was stabilized at pH = 9. This, H ⁺ ions generated by the water film between the membrane 115 and the anode plate 116 passes through the membrane 115 moves to the electrolysis chamber 113, OH of the electrolysis chamber 113 ^- to neutralize the reaction with ion Is thought to be the cause.

As Comparative Example 1, as shown in FIG. 9, an electrolytic cell having an electrolytic chamber 113 'also on the electrode plate 116 side and having a large distance (0.5 mm) between the electrode plate 116 and the diaphragm 115 was manufactured. As in 1, 4 liters of tap water with a pH of 7.2 and an ORP of +450 mV
Then, a voltage of 12 V was applied to perform electrolysis. The current flowing through both electrode plates 116 and 117 was 10 A (120 W). diaphragm
115 was the same as in Example 1, the distance between the electrode plates 116 and 117 was 1 mm, and the diaphragm 115 was set so as to be located at the center.

As a result, at the beginning of electrolysis, pH = 8-9, ORP = −200 mV
Was obtained. However, when this electrolysis was continued for 1 hour, pH and ORP started to fluctuate after 20 minutes as shown in FIGS. 7 and 8, and no further electrolysis was possible. This is considered to be because the inside of the electrolytic chamber 113 'was saturated with the electrolytically oxidized water.

Incidentally, in Example 2, the same electrolytic cell as in Example 1 was used, the polarity of the voltage applied to the electrode plates 116 and 117 was inverted, and the pH of the raw water to be electrolyzed was 7.4, the ORP was +350 mV, and the DO (dissolved oxygen amount) was 6.4 ppm. The electrolysis was performed under the same conditions as in Example 1 except that tap water was used. This was continued for one hour,
It was possible to obtain stable electrolytic oxidized water having a pH of 6.9, an ORP of +560 mV, and a DO of 10.0 ppm.

When the electrolytic cell of the fourth embodiment is implemented, various modes are conceivable. FIG. 10 is a longitudinal sectional view showing one example thereof, and FIG.
Is a longitudinal sectional view showing another example, and members common to the basic structure of the electrolytic cell of the present invention shown in FIG. 1 are denoted by the same reference numerals.

The electrolytic cell 11 shown in FIG. 10 has a casing 114 whose longitudinal section is formed in a rectangular parallelepiped shape. The lower end of the casing 114 has an inlet 111 for raw water to be electrolyzed (specifically, raw water An introduction pipe) is provided, and an outlet 112 for electrolytic water (specifically, a pipe for introducing electrolytic water) is provided at the upper end and also extends perpendicular to the plane of the drawing.

Further, a pair of electrode plates 116 and 117 are fixed in the electrolytic cell 11, and a diaphragm 115 is integrally attached to one of the electrode plates 116, for example. These electrode plates 11
7 and the diaphragm 115 become an electrolysis chamber 113, but a gap S is formed between the integrally formed diaphragm 115 and the electrode plate 116,
There will be water here too.

While assembling the electrode plate 116 and the diaphragm 115 integrally, in order to ensure watertightness with a gas chamber 119 described later,
A packing 151 is provided around the electrode plate 116 and the diaphragm 115.
Are fitted. Further, the other electrode plate 117 is
A packing 152 is also fitted around the electrode plate 117 in order to fix it to the casing 114.

In particular, in the electrolytic cell 11 of the present embodiment, the gas chamber 119 is formed outside the electrolytic chamber 113 so that the gas generated in the surface on the electrode plate 116 side, that is, the gas generated in the gap S can be efficiently collected in the gas chamber 119. It has become. “119a” is an outlet for discharging the gas released into the gas chamber 119 to a desired portion.

Incidentally, a chamber 119 ′ is also formed on the back surface of the electrode plate 117 that is not in contact with the diaphragm 115, but this is not essential and can be omitted, but by making the electrolytic cell 11 symmetrical. It can be preferably used to enhance compatibility between the anode and the cathode. For example, in the case of a device that can generate both electrolytic reduced water and electrolytic oxidized water, the electrode plate 116,
It is sufficient to provide a polarity inversion circuit in the application circuit to 117,
When this cannot be provided, it can be dealt with by replacing the electrode plate 117 with the unit of the electrode plate 116 and the diaphragm 115 shown in FIG. In this case, room 11
Since the outlet 119a 'opened at the top of 9' is unnecessary,
The plug may be closed by a plug 153 or the like.

On the other hand, in the electrolytic cell 11 shown in FIG. 11, a cylindrical casing 114 is employed. Further, in accordance with the cylindrical casing 114, the cylindrical electrode plate 1 having upper and lower ends opened.
16 and a cylindrical diaphragm 115 which is in contact with it and whose upper and lower ends are open. Further, in the center of the electrolytic chamber 113, for example, a solid electrode rod 117 is provided.

An inlet 111 for raw water to be electrolyzed is provided at a lower end of the electrolytic cell 11, and an outlet 112 for electrolyzed water is provided at an upper end. The raw water to be electrolyzed introduced from the inlet 111 is connected to an electrode rod 117 and a cylindrical After passing through a cylindrical electrolytic chamber 113 formed between the membrane 115 and the electrolyte, the electrolyte is taken out from the outlet 112.

Outside the electrolytic cell 11, the same gas chamber 119 as in the example shown in FIG.
15 and a cylindrical gap S formed by the cylindrical electrode plate 116
(Where a water film is formed)
It is discharged from the discharge port 119a.

The same operation and effect can be obtained by such a cylindrical electrolytic cell 11.

Fifth Embodiment The first to fourth embodiments described above are examples in which the present invention is applied to a water-permeable electrolytic cell, but the present invention can also be applied to a batch-type electrolytic cell. FIG. 12 is a conceptual diagram showing a basic configuration when the electrolytic cell of the present invention is applied to a batch type electrolytic cell, and members common to the basic configuration shown in FIG. 1 are denoted by the same reference numerals. Even with this type of batch type electrolytic cell, it is possible to produce electrolytic reduced water or electrolytic oxidized water having a large absolute value of the oxidation-reduction potential for a long time without depending on the intended characteristics, in particular, the pH value.

Sixth Embodiment An electrolyzed water generating apparatus provided with an electrolyzer according to the present invention supplies an electrolyzed water in real time and generates a large amount of electrolyzed water by circulating raw water to be electrolyzed into a storage tank. Can also be applied.

FIG. 13 is a view showing a sixth embodiment of the electrolyzed water generating apparatus of the present invention, in which the present invention is applied to a beverage.
Electrolytically reduced water can be used in place of drinking water used for home or business use. In this case, tap water is stored in a water storage tank 50 as shown in FIG. The water is led to the water generator 1 and subjected to the electrolysis as described above to generate electrolytic reduced water, which is returned to the water storage tank 50. If this circulation is continued for a certain time, pH
Is near neutral, and ORP is low.

More specifically, pH is 7.2, ORP is +450 mV, D
20 liters of tap water of which O is 7.0 is put into the water storage tank 50, and the pump is operated for 25 minutes using the electrolyzed water generation apparatus having the electrolysis tank described in the fourth embodiment, and the water in the water storage tank 50 is electrolyzed water. Electrolysis was performed while circulating through the generator 1.
The production rate of the electrolyzed water generator 1 was 4 liter / min, and the current flowing between the electrode plates was 10 A (constant). When the pH, ORP (mV), and DO (ppm) of the electrolyzed water stored in the water storage tank 50 were measured, the results shown in Table 3 were obtained, and electrolyzed water having a low ORP having an influence on the cleaning power was generated. Was.

The embodiments described above are described for facilitating the understanding of the present invention, and are not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tatsuya Naito 1-16-5 Yoshiyuki Fujisawa-shi, Kanagawa Miz Co., Ltd. (56) References JP-A 7-966 (JP, A) −5477 (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) C02F 1/46 C25B 9/00 WPI (DIALOG)

Claims (16)

(57) [Claims] 1. An electrolysis chamber into which raw water to be electrolyzed is introduced, one or more diaphragms partitioning the electrolysis chamber and the outside of the electrolysis chamber, and at least a diaphragm provided inside and outside the electrolysis chamber with the diaphragm interposed therebetween. An electrolytic cell having at least one electrode plate pair, wherein an electrode plate outside the electrolytic chamber is provided in contact with the diaphragm or with a small gap therebetween. 2. An electrolysis chamber into which raw water to be electrolyzed is introduced, two diaphragms provided so that main surfaces thereof face each other, and partitioning the electrolysis chamber and the outside of the electrolysis chamber; A pair of electrode plates provided so as to sandwich the two diaphragms, respectively, wherein the electrode plate outside the electrolytic chamber is provided in contact with the diaphragm or via a slight gap. Electrolyzer. 3. An electrolyzed water generating apparatus comprising: the electrolytic cell according to claim 1; and a power supply circuit for supplying an electrolytic voltage to the electrolytic cell. In the generation step, while applying a voltage of either the anode or the cathode to the electrode plate provided in the electrolytic chamber, the electrode plate provided outside the electrolytic chamber, the electrode plate provided in the electrolytic chamber An electrolyzed water generator characterized by applying a voltage having a polarity different from that of the electrolyzed water. 4. An electrolyzed water generating apparatus comprising: the electrolytic cell according to claim 2; and a power supply circuit that supplies an electrolytic voltage to the electrolytic cell. In the generating step, while applying a voltage of either the polarity of the anode or the cathode to the electrode plate provided in the electrolytic chamber, the electrode plate provided outside the electrolytic chamber, the electrode plate provided in the electrolytic chamber An electrolyzed water generator characterized by applying a voltage having a polarity different from that of the electrolyzed water. 5. The power supply circuit, in a backwashing step, applies a voltage having a different polarity to the electrode plate provided in the electrolysis chamber and applies a voltage to the electrode plate provided outside the electrolysis chamber. 4. The electrolyzed water generation apparatus according to claim 3, further comprising a backwashing circuit for applying a voltage having a polarity different from that of the electrode plate provided in the electrolysis chamber. 6. The power supply circuit applies a voltage having a polarity different from that of the electrolysis step to the electrode plate provided in the electrolysis chamber in the back washing step, and applies a voltage to the electrode plate provided outside the electrolysis chamber. The electrolyzed water generating apparatus according to claim 4, further comprising a backwashing circuit for applying a voltage having a polarity different from that of the electrode plate provided in the electrolysis chamber. 7. The power supply circuit is provided in the backwashing step with applying a voltage having a polarity different from that in the electrolyzed water generating step to one of the electrode plates provided in the electrolysis chamber, and provided in the electrolysis chamber. After applying a voltage having the same polarity as that of the electrolytic water generation step to the other of the electrode plates and performing the first reverse cleaning, the polarity of the voltage applied to both electrode plates provided in the electrolytic chamber is inverted. The electrolyzed water generating apparatus according to claim 4, further comprising a backwashing circuit for performing a second backwashing. 8. The apparatus according to claim 7, wherein said backwashing circuit does not apply a voltage to an electrode plate provided outside said electrolytic chamber during said first and second backwashing. Electrolyzed water generator. 9. The electrolytic cell according to claim 2, wherein one of the electrode plates outside the electrolytic chamber is provided in a second electrolytic chamber. 10. A first electrolysis chamber and a second electrolysis chamber into which raw water to be electrolyzed is introduced and partitioned by two diaphragms; and a first electrolysis chamber and a second electrolysis chamber, respectively.
A first electrolytic cell having two electrode plate pairs provided with the two diaphragms interposed therebetween; and electrolytic water generated in the first electrolytic chamber in the first electrolytic cell is introduced. A third electrolytic chamber, two diaphragms provided so that their main surfaces face each other, and partitioning the third electrolytic chamber and the outside of the third electrolytic chamber; Each having two electrode plate pairs provided with the two diaphragms interposed therebetween, wherein an electrode plate outside the third electrolytic chamber is provided in contact with the diaphragm or with a slight gap therebetween. An electrolytic cell, comprising: a second electrolytic cell; 11. The method according to claim 1, wherein the pair of electrode plates provided with the diaphragm interposed therebetween is constituted by a zero gap electrode.
Item 11. The electrolytic cell according to any one of Items 10. 12. A hole or a gap for allowing gas generated on the electrode surface to escape to the back side of the diaphragm is provided in at least one of the electrode plate pairs provided with the diaphragm interposed therebetween. The electrolytic cell according to any one of claims 1 to 2, or claims 9 to 11, characterized in that: 13. The method according to claim 1, wherein the electrode plate outside the electrolytic chamber is provided on the diaphragm so as to form an electrode film on a surface of the diaphragm.
The electrolytic cell according to any one of claims 9 to 12. 14. The electrode plate according to claim 1, wherein a noble metal coating is applied to a surface of said electrode plate. The electrolytic cell according to any one of the above. 15. An electrolytic cell according to any one of claims 1 to 2, or a combination of a plurality of electrolytic cells according to any one of claims 9 to 14, and the electrolytic cell. A water supply system for introducing raw water into each of the electrolysis chambers in parallel, and a water intake system for taking out the electrolyzed water generated in each of the electrolysis chambers in parallel. 16. An electrolytic cell according to any one of claims 1 to 2, or 9 to 14, and a power supply for supplying an electrolytic voltage to the electrolytic cell. A water storage tank that stores raw water to be electrolyzed, and a circulation system that returns the raw water to be electrolyzed in the water storage tank to the water storage tank and then returns to the water storage tank. And electrolysis is performed while circulating the raw water to be electrolyzed.